Process for dyeing unmodified polyolefin fibers with vat dyestuffs, leuco esters of vat dyestuffs or sulfur dyestuffs

ABSTRACT

Process for dyeing or printing unmodified polyolefin fibers with vat dyestuffs, leuco esters of vat dyestuffs or sulfur dyestuffs, by reacting under high-temperature dyeing conditions on these textile materials aqueous liquids or printing pastes containing the said dyestuffs in unvatted or vatted-up state or as vat acid, in the presence of a dispersion system on the basis of polyglycol ethers and, if required, converting the vatted products applied by reoxidation into their pigment form.

United States Patent von der Eltz et a1.

PROCESS FOR DYEING UNMODIFIED POLYOLEFIN FIBERS WITH VAT DYESTUFFS,LEUCO ESTERS OF VAT DYESTUFFS OR SULFUR DYESTUFFS Inventors: Hans-Ulrichvon der Eltz, Frankfurt am Main; Armand Lehinant,

Offenbach, Main; Hans-Peter Maier, Sulzbach, Taunus, all of GermanyHoechst Aktiengesellschaft, Frankfurt am Main, Germany Filed: Mar. 1,1973 Appl. No.: 336,901

Assignee:

Foreign Application Priority Data Mar. 7, 1972 Germany 2210877 US. Cl.8/37; 8/30; 8/34;

8/176; 8/180 Int. Cl D06p 1/30 Field of Search 8/30, 34, 37, 180, 176

References Cited UNITED STATES PATENTS 10/1962 Kutncr 8/34 OTHERPUBLICATIONS Cook, Handbook of Polyolefin Fibers, (1967), MerrowPublishing Co., Ltd. pp. 139-141.

Primary ExaminerBenjamin R. Padgett Assistant Examiner-B. Hunt Attorney,Agent, or Firm-Curtis, Morris & Safford [57] I ABSTRACT Process fordyeing or printing unmodified polyolefin fibers with vat dyestuffs,leuco esters of vat dyestuffs or sulfur dyestuffs, by reacting underhightemperature dyeing conditions on these textile materials aqueousliquids or printing pastes containing the said dyestuffs in unvatted orvatted-up state or as vat acid, in the presence of a dispersion systemon the basis of polyglycol ethers and, if required, converting thevatted products applied by reoxidation into their pigment form.

8 Claims, No Drawings PROCESS FOR DYEING UNMODIFIED POLYOLEFIN FIBERSWITH VAT DYESTUFFS, LEUCO ESTERS OF VAT DYESTUFFS OR SULFUR DYESTUFFSThe present invention relates to a process for the dyeing of unmodifiedpolyolefin fibers with vat dyes, leuco esters of vat dyes or sulfurdyes.

It is known that unmodified polyolefin fibers, for example,polypropylene fibers, are, generally, difficult to dye by direct dyeingmethods. Besides the immediate dyeing of the spinning mass in the meltwith pigment dyestuffs, the dyeing of piece goods made of such fiberswith aqueous suspensions of pigment dyestuffs and curable bindingsystems is described which form a correspondingly colored film layerfast to washing on the fiber surface when being heated. Disperse dyesused for dyeing polyester fibers and other hydrophobic fibers, however,yield under comparable thermal conditions only very fair dyeings whenbeing fixed, the yield of which is unproportioned with respect to theamount of dyestuff used.

Various methods for the modification of the polyolefin material allow toimprove the dye receptivity of the fiber considerably. For example,nitrogen-containing copolymers having a basic effect are introduced intothe spinning melt of the ground substance of which the fibers consistand so anchored in the macromolecule. The fibers so modified then haveaffinity towards the anionic dyestuffs. Polypropylene can also bemodified in such a manner that compounds of such metals which can formfast color lakes with metallizable dyestuffs are incorporated into themass or fiber. Thus, the fiber properties are influenced either by ametal-containing copolymer or by special after-treatment operations ofthe finished, unmodified fibrous material before dyeing, for example, asdescribed in German Auslegeschriften Nos. 1,297,577, 1,469,600 and1,619,601. But each of these processes for the modification ofpolyolefins requires additional operational expenditure which makes thefiber more expensive and sometimes inadvertantly affects the physicalproperties of the fiber, for example, by reducing its stability andelasticity or by increasing its inflammability.

It was, now found, that unmodified polyolefin fibers preferablypolypropylene fibers, can be dyed or printed with vat dyes, leuco estersof vat dyes, or sulfur dyes when allowing aqueous liquors or printingpastes containing the dyestuffs mentioned above in unvatted or vatted-upstate or as vat acid to act under hightemperature dyeing conditions onthese textile materials in the presence of a dispersion system on thebasis of polyglycol ethers and, if required, converting the vattedproducts applied by reoxidation to adopt their pigment form.

The present invention is based on the observation that vat dyes orsulfur dyes have a technically useful affinity towards the stronglyhydrophobic, unmodified polyolefin fibers when they are in theiroriginal unvatted form, as leuco dyestuff or as vat acid present in acertain colloidal state of dispersion and are applied under adequatethermal conditions which allow the diffusion into the fiber. Under theseconditions the concentration equilibrium of liquid to fiber can beshifted in favor of the fiber. The same applies to leuco esters of vatdyes when they are present as vat acid after acid saponification. Whenrespecting the conditions mentioned above, the dyeing or prints can beeffected according to the process claimed using the exhaustion method,the pad-steaming method or a printing method together with steamfixation of the dyes.

The exhaustion method requires temperatures within the range of from to135C, preferably about C, and a period of action of 40 to 70 minutes,preferably about 60 minutes; the pad-steaming and the print-steamingmethod require temperatures within the range of from 100 to C,preferably about 130C, and a period of action of from 10 to 40 minutes,preferably about 30 minutes. These temperatures suggested are, whilemaintaining a technical safety zone, below the range of temperature(from to C) at which the fiber melts.

The form of colloidal dispersion of the dyestuff which is essential forcarrying out the process of the invention can be obtained in thefollowing manner:

On the one hand by normal vatting as usually effected by means of sodiumdithionite and alkali or sodium sulfide for dyeing vat dyes or sulfurdyes on cellulose fibers, the excess amounts of chemicals in the bathbeing, however, smaller; on the other hand, the dyestuffs are dispersedin the desired manner which allows a diffusion into and thus anabsorption by the fiber, at best by means of an auxiliary mixture. Thisdispersion system essentially consists of a non-ionic auxiliary on thebasis of alkylor alkylaryl-polyglycol ethers or oxethylated fatty acidpolyglycol esters, preferably a reaction product of 1 mol of isotridecylalcohol with 8 mols of ethylene oxide, which is combined in theexhaustion method with anionic protective colloids having a dispersingeffect, preferably those on the basis of ligninsulfonic acid and,optionally, electrolyte in the form of sodium sulfate, and in thepad-steaming or printsteaming method with non-ionic protective colloidshaving a thickening effect, preferably a completely etherified locustbean flour.

In the thermal process, under high-temperature conditions or whensteaming under air-free conditions above 100C, the reduction agentsgradually lose their efficiency even with the exclusion of air, so thatthe leuco dye adopts the form of dispersion-under the action of thedispersing agent which enables the absorption. The same effect isobtained by the formation of the vat acid from solutions of the vattedvat dyestuffs or from leuco esters of the vat dyestuffs by adding acids.

When vatting is effected acid salts, preferably sodium hydrogen sulfite,may be added to the liquids. Sodium hydrogen sulfite avoids the possibleseparation of elementary sulfur from dithionite, sulfide or polysulfidewhile forming thiosulfate.

In the case of leuco esters of vat dyestuffs, the vat acid is formed inthe dyebath before the dyeing process itself by adding acetic acid(saponification of the ester without oxidation). The protective colloidon the basis of lignin-sulfonic acid which must concomitantly be usedhas the effect that the vat acid adopts the finely dispersed formdesired and has, thus, affinity towards the polyolefin fiber.

A colloidal dispersion of the dyestuffs to be used can also be obtainedby dissolving the pigment of the vat dyes or sulfur dyes in a suitablesolvent miscible with water, preferably dimethyl formamide, in a ratioof 1 z 3 to 1 10 of dyestuff to solvent, and by introducing thissolution in an aqueous bath containing the said protective colloid whilestirring. The fine pigment dispersion resulting therefrom grows coarserwhen heating the liquid to dyeing temperature which leads to the optimalstate of dispersion. When working by this method the followingreoxidation of the dyestuff is not required but the color yield issomewhat smaller than when dyeing from pure aqueous medium.

Within the process of the invention it cannot be avoided in all cases atwhich a dyestuff had been applied in its leuco form or as vat acid toeffect a reoxidation by oxidizing agents to convert the vatted dyestuffproduct into its original pigment state, because the hydrophobic natureof the polyolefin fiber does not allow a spontaneous autoxidation withair oxygen. For this purpose, preferably sodium nitrite or nitrous acidor sodium chlorite or chlorous acid are used, the acids having anoxidizing effect being freed from the corresponding salts by means ofacetic acid. The temperature to be used during the reoxidation processis within the range of from 100 to 1 C, preferably about 110C, the timesof action of the oxidizing agent are within about to 40 minutes. For thepurpose pointed out acetic acid has been chosen because it cannot beoxidized under the application conditions in contradistinction to theformic acid and because the pH it yields is not too low as it is, forexample, when using mineral acids. Acetic acid, furthermore, exercises acertain, if slight, swelling effect on the unmodified polypropylenefiber which is supposed to be the reason for the fact that thereoxidation temperature can be lower than the dyeing temperature itself.When reoxidizing, an overoxidation does not occur even with dyestuffsotherwise known for their sensibility towards nitrite or oxidation ifthe reoxidation temperature is controlled correspondingly.

To carry out the dyeings according to the new method suitable vatdyestuffs are those of the type of indigo, thioindigo and thecorresponding derivatives thereof, anthraquinone dyestuffs having one orseveral anthraquinone nuclei, of indanthrone, flavanthrone andanthraquinone carbazole, of acridones, (thio- )oxanthrones,pyranthrones, anthranthrones and anthrinides as well as ofdibenzanthrone and dibenzpyrenquinone, etc. The leuco esters of vatdyestuffs used in accordance with the invention are water-solubleproducts derived from the above-mentioned vat dyestuffs obtained byesterification, preferably with sulfuric acid. Sulfur dyes are meant tobe in the process of the present invention easily reducible,water-insoluble polymer substances which are obtained by melting organiccompounds, for example, aminophenols, nitrophenols, diaminobenzenes,diaminonaphthalenes, dinitronaphthalenes, etc., with sulfur, alkalimetal sulfides or alkali metal polysulfides and which representheterogeneous high-molecular weight mixtures with thiazine rings,thiazoles, disulfide chains, etc.

According to the process of the invention, the unmodified polyolefinfibers which are otherwise rather difficult to stain, could unexpectedlybe dyed with dyestuff assortments already dealt with in commerce undersimple conditions with corresponding color intensity depending on theamount of dyestuff used and having very good fastness to light and towet processing.

It is also surprising that a technically useful dispersion of the leucodyes, the vat acids or the pigment can be obtained with dispersionagents which have been applied for a long time in industry.

Finally, it wasalso surprising that the reoxidation of the leuco dyes orthe vat acids on the fiber occurs quantitatively without running therisk of over-oxidation of the dyestuff caused by the nitrous or chlorousacid (prepared from its sodium salts and acetic acid) under theconditions mentioned.

The following Examples illustrate the invention, the parts andpercentages are by weight, unless stated otherwise. TheColor-Index-Numbers indicated in the Examples to characterize thedyestuffs have been taken from the 2nd edition 1956 and the supplementvolume EXAMPLE 1 Flock material of unmodified polypropylene fibers wasdyed in a dyeing apparatus under high-temperature conditions, with agoods-to-liquor ratio of 1 20 at 125C for 60 minutes with an aqueousliquid which contained, calculated on the weight of the dry material,

2 percent of the vat dyestuff Vat Yellow 29 C.l.

No. 68,400, vatted according to the usual prescription with sodiumdithionite and sodium hydroxide solution, but avoiding excesses ofchemicals in the bath,

4 percent of an anionic protective colloid on the basis oflignin-sulfonic acid,

1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8mols of ethylene oxide and then rinsed with warm water.

In a second operational step, the leuco vat dyestuff absorbed by thefiber was reoxidized to yield the vat dyestuff by treating the material,first at 30C which temperature was increased within 1 hour to C, with agoods-to-liquor ratio of 1 20, with a fresh bath which contained perliter of water 2 g of sodium nitrite and 2 ml of acetic acid (60 Afterthe dyeing process the fibrous material so treated was rinsed and driedin usual manner.

A yellow dyeing of good fastness properties, especially of good fastnessto light and to wet processing, was obtained.

EXAMPLE 2 The dyeing was carried out in an analogous manner as describedin Example 1, using, however 2 percent of the vat dyestuff Vat Orange 7Color Index No. 71,105. A brilliant orange dyeing of very good fastnessproperties was obtained.

EXAMPLE 3 Dyeing was carried out in an analogous manner as described inExample 1, using, however 2 percent of the vat dyestuff Vat Red 14 ColorIndex No. 71,110. A brilliant scarlet dyeing of very good fastnessproperties was obtained.

EXAMPLE 4 Dyeing was carried out in an analogous manner as described inExample 1. The dyestuff used in this case was 2 percent of the vatdyestuff .Vat Red 15 Color Index No. 71,100. v V A wine-red dyeing ofvery good fastness properties was obtained.

EXAMPLE 5 Dyeing on the textile material was carried out in an analogousmanner as described in Example I using as dyestuff, however,

2 percent of the vat dyestuff Vat Blue 4 Color Index No. 69,800. Abrilliant solid blue dyeing was obtained.

EXAMPLE 6 When using 2 percent of the vat dyestuff Vat Green 1 ColorIndex No. 59,825 and dyeing in the same manner as described in Examplel, a brilliant bluish green dyeing of very good fastness properties wasobtained.

EXAMPLE 7 Dyeing was carried out in an analogous manner as described inExample 1, with the exception that after vatting the dyestuff the liquidwas acidified with 2 6 ml/l of an aqueous sodium hydrogensulfitesolution of 40Be' to form the finely dispersed vat acid.

A dyeing having the same quality as that described in Example 1 wasobtained.

EXAMPLE 8 After an adequate prewashing, piece goods of unmodifiedpolypropylene fibers were padded on the padding mangle with an aqueousliquor of room temperature containing per liter :1 suspension of 20 g ofvat dyestuff Vat Red 14 Color Index No.

71,1 in a micro-dispersed form,

10 g of a 2 percent aqueous solution of a completely etherified locustbean flour and 5 g of the reaction product of 1 mol of isotridecylalcohol with 8 mols of ethylene oxide, with a liquor-pick-up of 70percent, and dried. Then the material was cross-padded, with a liquorpick-up of 70 percent, with a liquid of room temperature which containedper liter of water 30 g of a reduction agent on the basis of a sulfinicacid derivative,

40 ml of sodium hydroxide solution of 32.5 percent (38B) and 15 g ofsodium sulfate (anhydrous) and steamed under high temperature conditionsat 130C for 15 minutes with the exclusion of air. The dyeing was thenbatched up, rinsed in the beam dyeing apparatus and reoxidized asdescribed in Example 1. A brilliant scarlet dyeing of good fastnessproperties was obtained.

EXAMPLE 9 Flock material of unmodified polypropylene fibers was dyed ona dyeing apparatus under hightemperature conditions, with agoods-to-liquor-ratio of l at 130C for 60 minutes with a liquid whichwas obtained as follows:

Calculated on the weight of the dry material 2 percent of the vatdyestuff Vat Blue 4 Color Index No. 69,800 were dissolved in 6 percentof dimethyl formamide (optionally by heating to about 40C and thissolution was introduced via a calico sieve into an aqueous bath of 40Cwhich contained 5 percent of an anionic protective colloid on the basisof lignin-sulfonic acid and 1 percent of the reaction product of 1 molof isotridecyl alcohol with 8 mols of ethylene oxide while stirringwhich yielded a fine dispersion.

After dyeing the material was rinsed with warm water.

A brilliant blue dyeing was obtained. Reoxidation as required in thecase of leuco dyes or vat acids is not necessary in this case, but thedyestuff yield is somewhat smaller than that obtained when dyeing frompure aqueous medium.

EXAMPLE l0 Piece-goods of unmodified polypropylene were padded, with aliquor-pick-up of percent at room temperature with a liquid that wasprepared in the following manner:

20 g per liter vat dyestuff Vat Green 1 Color Index No. 59,825 weredissolved in 60 ml of dimethyl formamide and the solution was introducedwith stirring into an aqueous bath which contained 5 g of the reactionproduct of 1 mol of isotridecyl alcohol with 8 mols of ethylene oxideand 10 g of a 2 percent aqueous solution of a completely etherifiedlocust bean flour.

The material so treated was steamed for 20 minutes at C in thehigh-temperature steaming apparatus without intermediate drying and thenrinsed with warm and cold water.

In the scope of the dyeing operation described, intermediate drying ispossible before steaming. However, reoxidation as described in Examples1 to 8 is not necessary in this case.

A brilliant green dyeing was obtained.

When proceeding by this method, prints can also be effected on thematerial.

EXAMPLE 1 1 Loose material of unmodified polypropylene fibers was dyed,with a goods-to-liquor ratio of 1 20, on a high-temperature dyeingapparatus at 130C for 60 minutes with a liquid which was prepared at 40Cin the following manner:

Calculated on the weight of the dry material,

2 percent of the leuco ester vat dyestuff Solubilized Vat Green 21 C].No. 59,051 were dissolved in warm water together with 5 percent of aprotective solloid on the basis of ligninsulfonic acid and 1 percent ofthe reaction product of 1 mol of isotridecyl alcohol with 8 mols ofethylene oxide and to that solution 1 percent of acetic acid (of 60percent) was added.

After dyeing the material so treated was rinsed with warm water and thevat acid absorbed was reoxidized on the fiber as described in Example 1.

A brilliant fast green dyeing of good yield was obtained.

EXAMPLE l2 Loose material of unmodified polypropylene fibers was dyed,with a goods-to-liquor ratio of l 20, on a dyeing apparatus for 60minutes with an aqueous liquid of 130C which contained, calculated onthe weight of the dry material, the following constituents:

2 percent of the sulfur dyestuff Sulphur Brown 51 C]. No. 53,327,

4 percent of crystallized sodium sulfide,

5 percent of an anionic protective colloid of the type oflignin-sulfonic acid,

1 percent of the reaction product of 1 mol of isotridecyl alcohol with 8mols of ethylene oxide and 20 percent of sodium sulfate (anhydrous).

After the application of the dyestuff the material so treated was firstrinsed with warm water and then it was treated for the reoxidation ofthe dyestuff at 105C for 20 minutes with an aqueous bath which contained1 g/l of sodium nitrite and 2 m/l of acetic acid (60 A fast brown dyeingwas obtained.

We claim:

1. A process for dyeing or printing unmodified polypropylene fibers withvat dyestuffs, leuco esters of vat dyestuffs or sulfur dyestuffs, whichcomprises: reacting under high-temperature dyeing conditions above 100Con these textile materials aqueous liquids or printing pastes containingthe said dyestuffs, in unvatted or vatted-up state or as vat acid, inthe presence of a dispersion system based upon polyglycol ethers oresters and, if required, converting the vatted products applied byreoxidation into their pigment form.

2. A process as claimed in claim 1, wherein: vat or sulfur dyestuffs arepadded or printed onto the fibers in vatted-up state and in the presenceof a non-ionic protective colloid having a thickening effect of the typeof a completely etherified locust bean flour; and these paddings orprints are then steamed in a pressure steamer at 100C to 135C for 10 to40 minutes and fi nally oxidized.

3. A process as claimed in claim 1, wherein: vat or sulfur dyestuffs areused in vatted-up state and in the presence of an anionic protectivecolloid having a dispersing effect based upon lignin-sulfonic acid; andthe dyestuffs are applied to the fibers in the finely dispersed form soobtained according to the exhaustion method, for 40 to 70 minutes at atemperature of 120 to 135C, and finally oxidized.

4. A process as claimed in claim 1, wherein: leuco esters of vatdyestuffs are used in the presence of an anionic protective colloidhaving a dispersing effect based upon lignin-sulfonic acid, by treatingthem with acetic acid while saponifying the esters without oxidation toyield the vat acid; and the dyestuffs are then applied to the fibers inthe finely dispersed form so obtained according to the exhaustionmethod, for 40 to minutes at a temperature of from 120 to 135C, andfinally oxidized.

5. A process as claimed in claim 1, wherein: leuco esters of vatdyestuffs are used in the presence of a nonionic protective colloidhaving a thickening effect of the type of a completely etherified locustbean flour, by treating them with acetic acid while saponifying theesters without oxidation to yield the vat acid; the dyestuffs are thenpadded or printed onto the fibers in the finely dispersed state soobtained; and these paddings or prints are then steamed in a pressuresteamer at to 135C for 10 to 40 minutes, and finally oxidized.

6. A process as claimed in claim 1, wherein the leuco dyestuff or thevat acid applied is reoxidized into its pigment form by treating thedyeings or prints with sodium nitrite or sodium chlorite in the presenceof acetic acid for 20 to 40 minutes at 100 to C.

7. A process as claimed in claim 1, wherein: vat or sulfur dyestuffs aredissolved, without vatting, in dimethyl formamide in a ratio of 1 3 to 1:10; the solution so obtained is introduced, while stirring, into anaqueous liquid together with an anionic protective colloid having adispersing effect based upon ligninsulfonic acid; and the dyestuffs areapplied to the fibers in the finely dispersed form so obtained accordingto the exhaustion method for 40 to 70 minutes at a temperature of fromto C.

8. A process as claimed in claim 1, wherein: vat or sulfur dyestuffs aredissolved, without vatting, in dimethyl formamide in a ratio of l 3 to l10; the solution so obtained is introduced, while stirring, into anaqueous liquid or printing paste together with a nonionic auxiliarybased upon the reaction product of 1 mol of isotridecyl alcohol with 8mols of ethylene oxide in combination with non-ionic protective colloidshaving a thickening effect of the type of a completely etherified locustbean flour; the dyestuffs are padded or printed onto the fibers in thefinely dispersed form so obtained; and these paddings or prints are thensteamed in a pressure steamer at 100 135C for 10 to 40 minutes.

1. A PROCESS FOR DYEING OR PRINTING UNMODIFIED POLYPROPYLENE FIBERS WITHVAT DYESTUFFS, LEUCO ESTERS OF VAT DYESTUFFS OR SULFUR DYESTUFFS, WHICHCOMPRISES: REACTING UNDER HIGH-TEMPERATURE DYEING CONDITIONS ABOVE 100*CON THESE TEXTILE MATERIALS AQUEOUS LIQUIDS OR PRINTING PASTES CONTAININGTHE SAID DYESTUFFS, IN UNVATTED OR VATTED-UP STATE OR AS VAT ACID, INTHE PRESENCE OF A DISPERSION SYSTEM BASED UPON POLYGLYCOL ETHERS ORESTERS AND, IF REQUIRED, CONVERTING THE VATTED PRODUCTS APPLIED BYREOXIDATION INTO THEIR PIGMENT FORM.
 2. A process as claimed in claim 1,wherein: vat or sulfur dyestuffs are padded or printed onto the fibersin vatted-up state and in the presence of a non-ionic protective colloidhaving a thickening effect of the type of a completely etherified locustbean flour; and these paddings or prints are then steamed in a pressuresteamer at 100*C to 135*C for 10 to 40 minutes and finally oxidized. 3.A process as claimed in claim 1, wherein: vat or sulfur dyestuffs areused in vatted-up state and in the presence of an anionic protectivecolloid having a dispersing effect based upon lignin-sulfonic acid; andthe dyestuffs are applied to the fibers in the finely dispersed form soobtained according to the exhaustion method, for 40 to 70 minutes at atemperature of 120* to 135*C, and finally oxidized.
 4. A process asclaimed in claim 1, wherein: leuco esters of vat dyestuffs are used inthe presence of an anionic protective colloid having a dispersing effectbased upon lignin-sulfonic acid, by treating them with acetic acid whilesaponifying the esters without oxidation to yield the vat acid; and thedyestuffs are then applied to the fibers in the finely dispersed form soobtained according to the exhaustion method, for 40 to 70 minutes at atemperature of from 120* to 135*C, and finally oxidized.
 5. A process asclaimed in claim 1, wherein: leuco esters of vat dyestuffs are used inthe presence of a non-ionic protective colloid having a thickeningeffect of the type of a completely etherified locust bean flour, bytreating them with acetic acid while saponifying the esters withoutoxidation to yield the vat acid; the dyestuffs are then padded orprinted onto the fibers in the finely dispersed state so obtained; andthese paddings or prints are then sTeamed in a pressure steamer at 100*to 135*C for 10 to 40 minutes, and finally oxidized.
 6. A process asclaimed in claim 1, wherein the leuco dyestuff or the vat acid appliedis reoxidized into its pigment form by treating the dyeings or printswith sodium nitrite or sodium chlorite in the presence of acetic acidfor 20 to 40 minutes at 100* to 115*C.
 7. A process as claimed in claim1, wherein: vat or sulfur dyestuffs are dissolved, without vatting, indimethyl formamide in a ratio of 1 : 3 to 1 :10; the solution soobtained is introduced, while stirring, into an aqueous liquid togetherwith an anionic protective colloid having a dispersing effect based uponlignin-sulfonic acid; and the dyestuffs are applied to the fibers in thefinely dispersed form so obtained according to the exhaustion method for40 to 70 minutes at a temperature of from 120* to 135*C.
 8. A process asclaimed in claim 1, wherein: vat or sulfur dyestuffs are dissolved,without vatting, in dimethyl formamide in a ratio of 1 : 3 to 1 : 10;the solution so obtained is introduced, while stirring, into an aqueousliquid or printing paste together with a non-ionic auxiliary based uponthe reaction product of 1 mol of isotridecyl alcohol with 8 mols ofethylene oxide in combination with non-ionic protective colloids havinga thickening effect of the type of a completely etherified locust beanflour; the dyestuffs are padded or printed onto the fibers in the finelydispersed form so obtained; and these paddings or prints are thensteamed in a pressure steamer at 100* - 135*C for 10 to 40 minutes.